U.S. patent application number 14/532465 was filed with the patent office on 2015-05-28 for method for printing three-dimensional parts wtih crystallization kinetics control.
The applicant listed for this patent is Stratasys, Inc.. Invention is credited to Vittorio L. Jaker, Luke M.B. Rodgers.
Application Number | 20150145168 14/532465 |
Document ID | / |
Family ID | 53181983 |
Filed Date | 2015-05-28 |
United States Patent
Application |
20150145168 |
Kind Code |
A1 |
Rodgers; Luke M.B. ; et
al. |
May 28, 2015 |
METHOD FOR PRINTING THREE-DIMENSIONAL PARTS WTIH CRYSTALLIZATION
KINETICS CONTROL
Abstract
A method for printing a three-dimensional part with an additive
manufacturing system, which includes providing a part material that
compositionally has one or more semi-crystalline polymers and one
or more secondary materials that are configured to retard
crystallization of the one or more semi-crystalline polymers, where
the one or more secondary materials are substantially miscible with
the one or more semi-crystalline polymers. The method also includes
melting the part material in the additive manufacturing system,
forming at least a portion of a layer of the three-dimensional part
from the melted part material in a build environment, and
maintaining the build environment at an annealing temperature that
is between a glass transition temperature of the part material and
a cold crystallization temperature of the part material.
Inventors: |
Rodgers; Luke M.B.; (Chaska,
MN) ; Jaker; Vittorio L.; (New Brighton, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Stratasys, Inc. |
Eden Prairie |
MN |
US |
|
|
Family ID: |
53181983 |
Appl. No.: |
14/532465 |
Filed: |
November 4, 2014 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61909611 |
Nov 27, 2013 |
|
|
|
Current U.S.
Class: |
264/308 |
Current CPC
Class: |
B33Y 10/00 20141201;
B29C 64/118 20170801; B29K 2079/085 20130101; B29K 2995/004
20130101; B29C 64/112 20170801; B29C 2071/022 20130101; B29K
2071/00 20130101; B29K 2995/0039 20130101; B29C 71/02 20130101;
B33Y 70/00 20141201; B29B 13/022 20130101; B29C 71/0063 20130101;
B29C 64/106 20170801; B29K 2105/0002 20130101; B29C 2035/1658
20130101; G03G 15/224 20130101; B29K 2105/0067 20130101; B33Y 50/02
20141201; B29K 2077/00 20130101; G03G 15/225 20130101 |
Class at
Publication: |
264/308 |
International
Class: |
B29C 67/00 20060101
B29C067/00 |
Claims
1. A method for printing a three-dimensional part with an additive
manufacturing system, the method comprising: providing a part
material compositionally including one or more semi-crystalline
polymers and one or more secondary materials that are configured to
retard crystallization of the one or more semi-crystalline
polymers, wherein the one or more secondary materials are
substantially miscible with the one or more semi-crystalline
polymers; melting the part material in the additive manufacturing
system; forming at least a portion of a layer of the
three-dimensional part from the melted part material in a build
environment; and maintaining the build environment at an annealing
temperature that is between a glass transition temperature of the
part material and a cold crystallization temperature of the part
material.
2. The method of claim 1, wherein the one or more secondary
materials comprise one or more amorphous polymers.
3. The method of claim 2, wherein the one or more amorphous
polymers constitute from about 50% by weight to about 85% by weight
of a combined weight of the one or more semi-crystalline polymers
and the one or more amorphous polymers.
4. The method of claim 1, wherein the one or more semi-crystalline
polymers comprise one or more semi-crystalline polyamides, and
wherein the one or more secondary materials comprise one or more
amorphous polyamides.
5. The method of claim 1, wherein the one or more semi-crystalline
polymers comprise one or more one or more polyaryletherketones, and
wherein the one or more secondary materials comprise one or more
polyetherimides.
6. The method of claim 1, and further comprising performing a
post-printing crystallization step on the printed three-dimensional
part.
7. The method of claim 1, wherein the one or more semi-crystalline
polymers are polymerized from one or more base monomers, and
wherein the one or more secondary materials comprise one or more
second semi-crystalline polymers polymerized from one or more
monomers that are isomers of the one or more base monomers.
8. The method of claim 7, wherein the one or more semi-crystalline
polymers and the one or more second semi-crystalline polymers each
comprise one or more polylactic acid polymers, one or more
polyetherketoneketone polymers, or one or more polyesters.
9. A method for printing a three-dimensional part from with an
additive manufacturing system, the method comprising: providing a
part material that compositionally comprises one or more
semi-crystalline polymers and one or more amorphous polymers that
are substantially miscible with the one or more semi-crystalline
polymers; maintaining a build environment of the additive
manufacturing system, at least in a deposition region of the build
environment, at an annealing temperature that is between a glass
transition temperature of the part material and a cold
crystallization temperature of the part material; feeding the part
material to a print head retained by of the additive manufacturing
system; melting the part material in the print head; extruding the
melted part material from the print head; and depositing the
extruded part material onto a build surface in the deposition
region to form at least a portion of a layer of the
three-dimensional part from the extruded part material.
10. The method of claim 9, wherein the one or more semi-crystalline
polymers comprise one or more semi-crystalline polyamides, and
wherein the one or more amorphous polymers comprise one or more
amorphous polyamides.
11. The method of claim 10, wherein the one or more amorphous
polymers constitute from about 50% by weight to about 85% by weight
of a combined weight of the one or more semi-crystalline polymers
and the one or more amorphous polymers.
12. The method of claim 8, and further comprising selecting the
annealing temperature to achieve a predetermined crystallinity
level for the part material of the printed three-dimensional
part.
13. The method of claim 8, wherein the one or more amorphous
polymers are configured to retard crystallization of the one or
more semi-crystalline polymers.
14. The method of claim 8, and further comprising performing a
post-printing crystallization step on the printed three-dimensional
part.
15. A method for printing a three-dimensional part with an additive
manufacturing system, the method comprising: providing a part
material that compositionally comprises one or more
semi-crystalline polymers and one or more amorphous polymers that
are substantially miscible with the one or more semi-crystalline
polymers; melting the part material in the additive manufacturing
system; forming layers of the three-dimensional part from the
melted part material using an additive manufacturing technique,
wherein the layers are formed in a region that is maintained at an
annealing temperature that is within 10.degree. C. of a glass
transition temperature of the part material; and reheating the
printed three-dimensional part to one or more temperatures that are
within about 10.degree. C. of a cold crystallization temperature of
the part material.
16. The method of claim 15, wherein the re-crystallization
temperature is within about 5.degree. C. of the cold
crystallization temperature of the part material.
17. The method of claim 15, wherein reheating the printed
three-dimensional part to the one or more temperatures is performed
for at least about 30 minutes.
18. The method of claim 15, wherein the reheating step is performed
in a separate oven from the additive manufacturing system.
19. The method of claim 18, and further comprising separating the
three-dimensional part from a build sheet used to received the
formed layers of the three-dimensional part.
20. The method of claim 15, wherein the one or more
semi-crystalline polymers comprise one or more semi-crystalline
polyamides, and wherein the one or more amorphous polymers comprise
one or more amorphous polyamides.
Description
CROSS-REFERENCE TO RELATED APPLICATION(S)
[0001] The present application claims priority to U.S. Provisional
Application No. 61/909,611, entitled "METHOD FOR PRINTING
THREE-DIMENSIONAL PARTS WTIH CRYSTALLIZATION KINETICS CONTROL", and
filed on Nov. 27, 2013.
BACKGROUND
[0002] The present disclosure relates to additive manufacturing
techniques for printing three-dimensional (3D) parts. In
particular, the present disclosure relates to additive
manufacturing methods for printing 3D parts in a layer-by-layer
manner from part materials having one or more semi-crystalline
polymeric materials.
[0003] Additive manufacturing systems are used to print or
otherwise build 3D parts from digital representations of the 3D
parts (e.g., AMF and STL format files) using one or more additive
manufacturing techniques. Examples of commercially available
additive manufacturing techniques include extrusion-based
techniques, jetting, selective laser sintering, powder/binder
jetting, electron-beam melting, and stereolithographic processes.
For each of these techniques, the digital representation of the 3D
part is initially sliced into multiple horizontal layers. For each
sliced layer, a tool path is then generated, which provides
instructions for the particular additive manufacturing system to
print the given layer.
[0004] For example, in an extrusion-based additive manufacturing
system, a 3D part may be printed from a digital representation of
the 3D part in a layer-by-layer manner by extruding a flowable part
material. The part material is extruded through an extrusion tip
carried by a print head of the system, and is deposited as a
sequence of roads on a substrate in an x-y plane. The extruded part
material fuses to previously deposited part material, and
solidifies upon a drop in temperature. The position of the print
head relative to the substrate is then incremented along a z-axis
(perpendicular to the x-y plane), and the process is then repeated
to form a 3D part resembling the digital representation.
[0005] In fabricating 3D parts by depositing layers of a part
material, supporting layers or structures are typically built
underneath overhanging portions or in cavities of 3D parts under
construction, which are not supported by the part material itself.
A support structure may be built utilizing the same deposition
techniques by which the part material is deposited. The host
computer generates additional geometry acting as a support
structure for the overhanging or free-space segments of the 3D part
being formed. Support material is then deposited from a second
nozzle pursuant to the generated geometry during the printing
process. The support material adheres to the part material during
fabrication, and is removable from the completed 3D part when the
printing process is complete.
SUMMARY
[0006] An aspect of the present disclosure is directed to a method
for printing a 3D part with an additive manufacturing system. The
method includes providing a part material that compositionally
includes one or more semi-crystalline polymers and one or more
secondary materials that are configured to retard crystallization
of the one or more semi-crystalline polymers, where the one or more
secondary materials are substantially miscible with the one or more
semi-crystalline polymers. The method also includes melting the
part material in the additive manufacturing system, forming at
least a portion of a layer of the 3D part from the melted part
material in a build environment, and maintaining the build
environment at an annealing temperature that is between a glass
transition temperature of the part material and a cold
crystallization temperature of the part material.
[0007] Another aspect of the present disclosure is directed to a
method for printing a 3D part from with an additive manufacturing
system, where the method includes providing a part material that
compositionally comprises one or more semi-crystalline polymers and
one or more amorphous polymers that are substantially miscible with
the one or more semi-crystalline polymers. The method also includes
maintaining a build environment of the additive manufacturing
system, at least in a deposition region of the build environment,
at an annealing temperature that is between a glass transition
temperature of the part material and a cold crystallization
temperature of the part material. The method also includes feeding
the part material to a print head retained by of the additive
manufacturing system, melting the part material in the print head,
extruding the melted part material from the print head, and
depositing the extruded part material onto a build surface in the
deposition region to form at least a portion of a layer of the 3D
part from the extruded part material.
[0008] Another aspect of the present disclosure is directed to a
method for printing a 3D part from with an additive manufacturing
system, where the method includes providing a part material that
compositionally comprises one or more semi-crystalline polymers and
one or more amorphous polymers that are substantially miscible with
the one or more semi-crystalline polymers. The method also includes
melting the part material in the additive manufacturing system,
forming layers of the three-dimensional part from the melted part
material using an additive manufacturing technique, wherein the
layers are formed in a region that is maintained at an annealing
temperature that is similar to a glass transition temperature of
the part material (e.g., within about 10.degree. C.), and reheating
the printed three-dimensional part to one or more temperatures that
are within a small range of a cold crystallization temperature of
the part material (e.g., within about 10.degree. C.).
[0009] Another aspect of the present disclosure is directed to a
method for printing a 3D part from with a selective laser sintering
system. The method includes providing a part material that
compositionally comprises one or more semi-crystalline polymers and
one or more amorphous polymers that are substantially miscible with
the one or more semi-crystalline polymers. The methods also
includes forming layers of the 3D part from the part material using
the selective laser sintering system, and maintaining an
environmental temperature for the formed layers that is between a
hot crystallization temperature of the part material and a melting
temperature of the part material.
DEFINITIONS
[0010] Unless otherwise specified, the following terms as used
herein have the meanings provided below:
[0011] The term "polymer" refers to a polymeric material having one
or more monomer species, including homopolymers, copolymers,
terpolymers, and the like.
[0012] The term "semi-crystalline polymer" refers to a polymer
capable of exhibiting an average percent crystallinity in a solid
state of at least about 10% by weight when allowed to crystallize
to its fullest extent. The term "semi-crystalline polymer" includes
polymeric materials capable of having crystallinities up to 100%
(i.e., fully-crystalline polymeric materials). The term "amorphous
polymer" refers to a polymer that is not a semi-crystalline
polymer.
[0013] Reference to "a" chemical compound refers one or more
molecules of the chemical compound, rather than being limited to a
single molecule of the chemical compound. Furthermore, the one or
more molecules may or may not be identical, so long as they fall
under the category of the chemical compound. Thus, for example, "a"
polyamide is interpreted to include one or more polymer molecules
of the polyamide, where the polymer molecules may or may not be
identical (e.g., different molecular weights and/or isomers).
[0014] The terms "at least one" and "one or more of" an element are
used interchangeably, and have the same meaning that includes a
single element and a plurality of the elements, and may also be
represented by the suffix "(s)" at the end of the element. For
example, "at least one polyamide", "one or more polyamides", and
"polyamide(s)" may be used interchangeably and have the same
meaning.
[0015] Directional orientations such as "above", "below", "top",
"bottom", and the like are made with reference to a layer-printing
direction of a 3D part. In the embodiments shown below, the
layer-printing direction is the upward direction along the vertical
z-axis. In these embodiments, the terms "above", "below", "top",
"bottom", and the like are based on the vertical z-axis. However,
in embodiments in which the layers of 3D parts are printed along a
different axis, such as along a horizontal x-axis or y-axis, the
terms "above", "below", "top", "bottom", and the like are relative
to the given axis.
[0016] Unless otherwise specified, characteristics of a material or
a 3D part printed from the material refer to the characteristics as
measured parallel to the orientation of the 3D part layers and
perpendicular to the layer-printing direction, and is referred to
as an "xy-direction". Correspondingly, the term "z-direction", with
reference to characteristics of a material or a 3D part printed
from the material refer to the characteristics as measured
perpendicular to the orientation of the 3D part layers and parallel
to the layer-printing direction. Unless the measurement direction
is specified as "in the z-direction", a measurement referred to
herein is taken in the xy-direction. For example, a tensile
strength of a 3D part of 10,000 psi refers to a tensile strength
measured parallel to the layers of the 3D part. Alternatively, a
tensile strength of a 3D part in the z-direction of 8,000 psi
refers to a tensile strength measured perpendicular to the layers
of the 3D part.
[0017] Unless otherwise specified, temperatures referred to herein
are based on atmospheric pressure (i.e. one atmosphere).
[0018] The term "additive manufacturing system" refers to a system
that prints, builds, or otherwise produces 3D parts and/or support
structures at least in part using an additive manufacturing
technique. The additive manufacturing system may be a stand-alone
unit, a sub-unit of a larger system or production line, and/or may
include other non-additive manufacturing features, such as
subtractive-manufacturing features, pick-and-place features,
two-dimensional printing features, and the like.
[0019] The term "providing", such as for "providing a consumable
material", when recited in the claims, is not intended to require
any particular delivery or receipt of the provided item. Rather,
the term "providing" is merely used to recite items that will be
referred to in subsequent elements of the claim(s), for purposes of
clarity and ease of readability.
[0020] The terms "preferred" and "preferably" refer to embodiments
of the invention that may afford certain benefits, under certain
circumstances. However, other embodiments may also be preferred,
under the same or other circumstances. Furthermore, the recitation
of one or more preferred embodiments does not imply that other
embodiments are not useful, and is not intended to exclude other
embodiments from the scope of the present disclosure.
[0021] The terms "about" and "substantially" are used herein with
respect to measurable values and ranges due to expected variations
known to those skilled in the art (e.g., limitations and
variabilities in measurements).
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a front view of an additive manufacturing system
configured to print 3D parts pursuant to the method of the present
disclosure.
[0023] FIG. 2 is a front view of a print head of the additive
manufacturing system.
[0024] FIG. 3 is an expanded sectional view of a drive mechanism, a
liquefier assembly, and a nozzle of the print head.
[0025] FIG. 4 is an illustrative differential scanning calorimetry
(DSC) plot of heat flow versus temperature for a part material.
[0026] FIG. 5 is a photograph of printed 3D parts and pellets from
a PEEK/PEI part material.
[0027] FIG. 6 is a graphical illustration of modulus versus
temperature for example PET part materials printed in heated
chambers having different annealing temperatures.
[0028] FIG. 7 is a graphical illustration of the tan-delta results
for the example PET part materials shown in FIG. 6.
[0029] FIG. 8 is a graphical illustration of modulus versus
temperature for example PET part materials, illustrating
crystallization effects of a post-printing crystallization
process.
DETAILED DESCRIPTION
[0030] The present disclosure is directed to an additive
manufacturing method for printing 3D parts in a layer-by-layer
manner from a part material that, in a preferred embodiment,
compositionally includes a blend of one or more semi-crystalline
polymers and one or more secondary materials that retard
crystallization of the semi-crystalline polymer(s), such as one or
more amorphous polymers that are at least partially miscible with
the semi-crystalline polymer(s). In particular, the method involves
controlling the crystallization kinetics of the semi-crystalline
polymer(s) upon cooling from a melted state to minimize or
otherwise reduce the percent crystallinity of the printed part
material, while also generating enough crystallization-exothermic
energy to induce molecular reptation at the extrudate-part
interface.
[0031] As discussed below, the manner in which the crystallization
kinetics of the part material are controlled can vary depending on
the additive manufacturing technique used, such as an
extrusion-based additive manufacturing technique, an
electrophotography-based additive manufacturing technique, or a
selective laser sintering technique. These distinctions are
primarily due to the different thermal states in which the printed
layers are typically held for the given additive manufacturing
techniques. As such, the following discussion initially focuses on
controlling the crystallization kinetics in an extrusion-based
additive manufacturing system, and the applications for use in an
electrophotography-based additive manufacturing and a selective
laser sintering system will be subsequently discussed.
[0032] Extrusion-based additive manufacturing systems typically
print or otherwise build 3D parts from amorphous polymeric
materials, such as acrylonitrile-butadiene-styrene (ABS) resins and
polycarbonate resins. During a printing operation, the amorphous
polymeric material is melted and extruded as a series of roads,
which cool down to form layers of a 3D part. Due to the
layer-by-layer nature of the printing, the cooling of each
successive layer generates residual stresses in the 3D part, which
are a function of the coefficient of thermal expansion, percent
shrinkage, and tensile modulus of the material. If not relieved,
the residual stresses may physically distort the 3D part, such as
by causing the edges and corners of the 3D part to curl up,
referred to as "curl" or "curling".
[0033] Amorphous polymeric materials have little or no ordered
arrangements of their polymer chains in their solid states. As
such, these materials exhibit glass transition effects that can be
controlled to partially relieve residual stresses. For example, as
disclosed in Batchelder, U.S. Pat. No. 5,866,058, an amorphous
polymeric material may be deposited into a heated chamber (or at
least a locally-heat deposition region) maintained at a temperature
that is between a solidification temperature and a glass transition
temperature of the material. This anneals the successively-printed
printed layers, allowing them to cool down and solidify slowly,
which can partially relieve the residual stresses.
[0034] Semi-crystalline polymeric materials, however, have
different mechanical and thermal characteristics from amorphous
polymeric materials. For example, due to their achievable
crystallinity, 3D parts printed with semi-crystalline polymeric
materials may exhibit superior mechanical properties compared to 3D
parts printed with amorphous polymeric materials. However, due to
their higher levels of achievable crystallinity, semi-crystalline
polymeric materials can exhibit discontinuous changes in volume
upon solidification. Therefore, layers of a semi-crystalline
polymeric material may contract and shrink when deposited, thereby
accumulating residual stresses.
[0035] In comparison to amorphous polymeric materials, which can
have relatively broad annealing windows, it has been conventionally
difficult to maintain a temperature window that is suitable for
annealing semi-crystalline polymers, particularly with
extrusion-based additive manufacturing systems. For instance, curl
will result if we hold the polymer above the window, as will curl
result if below the window. Any variations outside of this small
temperature window will result in solidification with discontinuous
changes in volume, such as curl, if above or below the temperature
window. The discontinuous changes in volume can be particularly
troublesome for extrusion-based additive manufacturing systems
where the printed 3D parts or support structures are coupled to
underlying and non-shrinkable build sheets. Furthermore, sagging
may occur if there is not enough crystallinity generated during the
cooling process. Each of these conditions may result in distortions
of the printed 3D part. As such, it has been difficult to print
dimensionally stable 3D parts from semi-crystalline polymers using
extrusion-based additive manufacturing systems, where the amount of
crystallinity formed during the cooling process is sufficient such
that the 3D parts do not sag, yet also do not induce curl forces
that will curl the 3D part.
[0036] However, as discussed below, the crystallization kinetics of
particular part materials can be controlled in an extrusion-based
additive manufacturing system to print 3D parts having mechanical
properties (e.g., strengths and ductilities) similar to those of
semi-crystalline polymeric materials, while also being annealable
in a heated chamber of an additive manufacturing system (or at
least a locally-heated deposition region) to partially relieve
residual stresses.
[0037] FIGS. 1-3 illustrate system 10, which is an example
extrusion-based additive manufacturing system for printing or
otherwise building 3D parts, from the part material blends
discussed herein, in a manner that controls the crystallization
kinetics, as discussed below. Suitable extrusion-based additive
manufacturing systems for system 10 include fused deposition
modeling systems developed by Stratasys, Inc., Eden Prairie, Minn.
under the trademark "FDM".
[0038] As shown in FIG. 1, system 10 may include chamber 12, platen
14, platen gantry 16, print head 18, head gantry 20, and consumable
assemblies 22 and 24. Chamber 12 is an example enclosed build
environment that contains platen 14 for printing 3D parts and
support structures, where chamber 12 may be may be optionally
omitted and/or replaced with different types of build environments.
For example, a 3D part and support structure may be built in a
build environment that is open to ambient conditions or may be
enclosed with alternative structures (e.g., flexible curtains).
[0039] In the shown example, the interior volume of chamber 12 may
be heated with heater 12h to reduce the rate at which the part and
support materials solidify after being extruded and deposited
(e.g., to reduce distortions and curling). Heater 12h may be any
suitable device or assembly for heating the interior volume of
chamber 12, such as by radiant heating and/or by circulating heated
air or other gas (e.g., inert gases). In alternative embodiments,
heater 12h may be replaced with other conditioning devices, such as
a cooling unit to generate and circulate cooling air or other gas.
The particular thermal conditions for the build environment may
vary depending on the particular consumable materials used.
[0040] In further embodiments, the heating may be localized rather
than in an entire chamber 12. For example, the deposition region
may be heated in a localized manner. Example techniques for
locally-heating a deposition region include heating platen 14
and/or with directing heat air jets towards platen 14 and/or the 3D
parts/support structures being printed). As discussed above, the
heating in chamber 12 and/or the localized deposition region
anneals the printed layers of the 3D parts (and support structures)
to partially relieve the residual stresses, thereby reducing
curling of the 3D parts.
[0041] Platen 14 is a platform on which 3D parts and support
structures are printed in a layer-by-layer manner. In some
embodiments, platen 14 may also include a flexible polymeric film
or liner on which the 3D parts and support structures are printed.
In the shown example, print head 18 is a dual-tip extrusion head
configured to receive consumable filaments from consumable
assemblies 22 and 24 (e.g., via guide tubes 26 and 28) for printing
3D part 30 and support structure 32 on platen 14. Consumable
assembly 22 may contain a supply of the part material for printing
3D part 30 from the part material. Consumable assembly 24 may
contain a supply of a support material for printing support
structure 32 from the given support material.
[0042] Platen 14 is supported by platen gantry 16, which is a
gantry assembly configured to move platen 14 along (or
substantially along) a vertical z-axis. Correspondingly, print head
18 is supported by head gantry 20, which is a gantry assembly
configured to move print head 18 in (or substantially in) a
horizontal x-y plane above chamber 12.
[0043] In an alternative embodiment, platen 14 may be configured to
move in the horizontal x-y plane within chamber 12, and print head
18 may be configured to move along the z-axis. Other similar
arrangements may also be used such that one or both of platen 14
and print head 18 are moveable relative to each other. Platen 14
and print head 18 may also be oriented along different axes. For
example, platen 14 may be oriented vertically and print head 18 may
print 3D part 30 and support structure 32 along the x-axis or the
y-axis.
[0044] System 10 also includes controller 34, which is one or more
control circuits configured to monitor and operate the components
of system 10. For example, one or more of the control functions
performed by controller 34 can be implemented in hardware,
software, firmware, and the like, or a combination thereof.
Controller 34 may communicate over communication line 36 with
chamber 12 (e.g., with a heating unit for chamber 12), print head
18, and various sensors, calibration devices, display devices,
and/or user input devices.
[0045] In some embodiments, controller 34 may also communicate with
one or more of platen 14, platen gantry 16, head gantry 20, and any
other suitable component of system 10. While illustrated as a
single signal line, communication line 36 may include one or more
electrical, optical, and/or wireless signal lines, allowing
controller 34 to communicate with various components of system 10.
Furthermore, while illustrated outside of system 10, controller 34
and communication line 36 may be internal components to system
10.
[0046] System 12 and/or controller 34 may also communicate with
computer 38, which is one or more computer-based systems that
communicates with system 12 and/or controller 34, and may be
separate from system 12, or alternatively may be an internal
component of system 12. Computer 38 includes computer-based
hardware, such as data storage devices, processors, memory modules
and the like for generating and storing tool path and related
printing instructions. Computer 38 may transmit these instructions
to system 10 (e.g., to controller 34) to perform printing
operations. Controller 34 and computer 38 may collectively be
referred to as a controller assembly for system 10.
[0047] FIG. 2 illustrates a suitable device for print head 18, as
described in Leavitt, U.S. Pat. No. 7,625,200. Additional examples
of suitable devices for print head 18, and the connections between
print head 18 and head gantry 20 include those disclosed in Crump
et al., U.S. Pat. No. 5,503,785; Swanson et al., U.S. Pat. No.
6,004,124; LaBossiere, et al., U.S. Pat. Nos. 7,384,255 and
7,604,470; Batchelder et al., U.S. Pat. No. 7,896,209; and Comb et
al., U.S. Pat. No. 8,153,182. In additional embodiments, in which
print head 18 is an interchangeable, single-nozzle print head,
examples of suitable devices for each print head 18, and the
connections between print head 18 and head gantry 20 include those
disclosed in Swanson et al., U.S. Patent Application Publication
No. 2012/0164256.
[0048] In the shown dual-tip embodiment, print head 18 includes two
drive mechanism 40 and 42, two liquefier assemblies 44 and 46, and
two nozzles 48 and 50. In this embodiment the part material and the
support material each preferably have a filament geometry for use
with print head 18. For example, as best shown in FIG. 3, the part
material may be provided as filament 52. In alternative
embodiments, the part material of the present disclosure may be
provided in powder or pellet form for use in an auger-pump print
head, such as disclosed in Bosveld et al., U.S. Publication No.
2013/0333798.
[0049] During operation, controller 34 may direct wheels 54 of
drive mechanism 40 to selectively draw successive segments filament
52 from consumable assembly 22 (via guide tube 26), and feed
filament 52 to liquefier assembly 44. Liquefier assembly 44 may
include liquefier tube 56, thermal block 58, heat shield 60, and
tip shield 62, where liquefier tube 56 includes inlet end 64 for
receiving the fed filament 52. Nozzle 48 and tip shield 62 are
accordingly secured to outlet end 66 of liquefier tube 56, and
liquefier tube 56 extends through thermal block 58 and heat shield
60.
[0050] While liquefier assembly 44 is in its active state, thermal
block 58 heats liquefier tube 56 to define heating zone 68. The
heating of liquefier tube 56 at heating zone 68 melts the part
material of filament 52 in liquefier tube 56 to form melt 70. The
upper region of liquefier tube 56 above heating zone 68, referred
to as transition zone 72, is not directly heated by thermal block
58. This generates a thermal gradient or profile along the
longitudinal length of liquefier tube 56.
[0051] The molten portion of the part material (i.e., melt 70)
forms meniscus 74 around the unmelted portion of filament 52.
During an extrusion of melt 70 through nozzle 48, the downward
movement of filament 52 functions as a viscosity pump to extrude
the part material of melt 70 out of nozzle 48 as extruded roads to
print 3D part 30 in a layer-by-layer manner. While thermal block 58
heats liquefier tube 56 at heating zone 68, cooling air may also be
blown through a manifold 76 toward inlet end 64 of liquefier tube
56, as depicted by arrows 78. Heat shield 60 assists in directing
the air flow toward inlet end 64. The cooling air reduces the
temperature of liquefier tube 56 at inlet end 64, which prevents
filament 52 from softening or melting at transition zone 72.
[0052] In some embodiments, controller 34 may servo or swap
liquefier assemblies 44 and 46 between opposing active and stand-by
states. For example, while liquefier assembly 46 is servoed to its
active state for extruding the support material to print a layer of
support structure 32, liquefier assembly 44 is switched to a
stand-by state to prevent the part material from being extruded
while liquefier assembly 46 is being used. After a given layer of
the support material is completed, controller 34 then servoes
liquefier assembly 46 to its stand-by state, and switches liquefier
assembly 44 to its active state for extruding the part material to
print a layer of 3D part 30. This servo process may be repeated for
each printed layer until 3D part 30 and support structure 32 are
completed.
[0053] While liquefier assembly 46 is in its active state for
printing support structure 32 from a support material filament,
drive mechanism 42, liquefier assembly 46, and nozzle 50 (each
shown in FIG. 2) may operate in the same manner as drive mechanism
40, liquefier assembly 44, and nozzle 48 for extruding the support
material. In particular, drive mechanism 40 may draw successive
segments of the support material filament from consumable assembly
24 (via guide tube 28), and feed the support material filament to
liquefier assembly 46. Liquefier assembly 46 thermally melts the
successive segments of the received support material filament such
that it becomes a molten support material. The molten support
material may then be extruded and deposited from nozzle 50 as a
series of roads onto platen 14 for printing support structure 32 in
a layer-by-layer manner in coordination with the printing of 3D
part 30.
[0054] As mentioned above, the part material compositionally
includes a blend of one or more semi-crystalline polymers and one
or more secondary materials that retard crystallization of the
semi-crystalline polymer(s). Preferably, the secondary material(s)
include one or more amorphous polymers that are at least partially
miscible with the semi-crystalline polymer(s). The following
discussion is made with reference to the secondary material(s) as
amorphous polymer(s) with the understanding that the part material
may alternatively include other non-amorphous polymer(s) to retard
crystallization of the semi-crystalline polymer(s). Nonetheless,
amorphous polymer(s) are preferred as they may also provide
additional desired characteristics to the part material.
[0055] More preferably, the semi-crystalline polymer(s) and the
amorphous polymer(s) are substantially miscible with each other.
The substantially miscible blend may exhibit a co-continuous phase
of the semi-crystalline polymer(s) and the amorphous polymer(s), or
more preferably a single continuous phase of the semi-crystalline
polymer(s) and the amorphous polymer(s). While not wishing to be
bound by theory, it is believed that this miscibility allows the
amorphous polymer(s) to physically impede the semi-crystalline
polymer(s) from forming crystalline regions, which accordingly
retards crystallization.
[0056] In some embodiments, the amorphous polymer(s) of the part
material have substantially no measurable melting points (less than
5 calories/gram) using differential scanning calorimetry (DSC)
pursuant to ASTM D3418-08. Correspondingly, in these embodiments,
the semi-crystalline polymer(s) of the part material have
measureable melting points (5 calories/gram or more) using DSC
pursuant to ASTM D3418-08. As discussed below, the part material
may also optionally include one or more additives dispersed in the
blend.
[0057] FIG. 4 illustrates a DSC plot for an exemplary part material
of the present disclosure having a substantially miscible blend of
one or more semi-crystalline polymers and one or more amorphous
polymers. The DSC pot in FIG. 4 shows the various thermal
transitions that the part material may exhibit. For example, during
an initial heating phase, such as when the part material is melted
in liquefier assembly 44, the part material may produce a heating
profile 80 with a glass transition temperature (T.sub.g), a cold
crystallization temperature (T.sub.c,cold), and a melting
temperature (T.sub.m). The glass transition temperature (T.sub.g)
refers to the point along curve 80 where the part material
undergoes a second-order transition to achieve an increase in its
heat capacity.
[0058] In some embodiments, the semi-crystalline copolymer or blend
may consist essentially of semi-crystalline polymers that exhibit
substantial or complete miscibility. This may be the case for
closely related polymers that are synthesized using (i) one or more
base monomers, and (ii) a sizable fraction of one or more monomers
that are structural or optical isomers of the base monomer(s)
usually used in the synthesis. Other options include additional,
unrelated monomers added in sufficient amounts to substantially
alter the glass transition temperature, crystallization
temperatures, re-crystallization temperatures, melting points,
and/or enthalpies of fusion, as measured during heating or cooling
at a specified, constant rate.
[0059] Examples of some suitable techniques for these embodiments
include controlling the level of d-lactide and l-lactide
incorporated into a final polylactic acid polymer to achieve a
poly-DL-lactide. The DL polylactic acid copolymer has slower
crystallization kinetics and may even exhibit characteristics of a
completely amorphous polymer.
[0060] Another useful example includes polyetherketoneketone
(PEKK). Crystallinity, melting, point, enthalpy of fusion,
crystallization rate, and even glass transition temperature have
been seen to drop as the ratio of terephthalic
moieties-to-isophtalic moieties in the copolymer backbone
increases. In PEKK, an observed range from highly crystalline to
practically amorphous behavior is observed in
terephthalic-to-isophtalic moiety ratios from about 80/20 to about
60/40.
[0061] A third useful example includes the synthesis of polyesters,
specifically those based on a poly(ethyleneterephthalate) polymer.
In this case, some isophthalic moeities may be used in place of a
terephthalic moeities to impart similar adjustments in
crystallinity and crystallization behavior as discussed above for
PEKK. Additionally, one or more glycols may be exchanged with one
or more ethylene glycols, propylene glycols, and/or butylene
glycols, such as cyclohexanedimethanol, for example, to achieve
similar effects.
[0062] The cold crystallization temperature T.sub.c,cold typically
occurs due to the increased mobility of the polymer molecules after
exceeding the glass transition temperature T.sub.g, which allows a
portion of the semi-crystalline polymer(s) to form crystalline
regions. Because the crystallization is an exothermic process, it
releases thermal energy based on a first-order transition, as
illustrated by the inverted peak in heating profile 80.
[0063] The melting temperature T.sub.m is the temperature at which
the part material fully liquefies, also based on a first-order
transition. Typically, the part material is quickly heated past its
melting temperature T.sub.m in liquefier assembly 44 for extrusion.
As such, during this point in the process, the glass transition
temperature T.sub.g and the cold crystallization temperature
T.sub.c,cold are not overly relevant to the crystallization state
of the extrudate, other than for potential melt flow and
temperature control aspects in liquefier assembly 44.
[0064] The DSC plot in FIG. 4 also includes a cooling profile 82,
which illustrates hot crystallization temperature T.sub.c,hot, and
describes the crystallization kinetics of the part material as it
cools down from its melting temperature T.sub.m. For example, after
being extruded from nozzle 48, the extruded part material may
deposit as roads onto the previously-formed layer of 3D part 30,
and begin cooling down. In other words, the part material begins to
follow cooling profile 82 at a cooling rate that depends on the
environment temperature that 3D part 30 is printed in (e.g. in
chamber 12), as well as the particular composition of the part
material and the size of 3D part 30.
[0065] Preferably, the layers of 3D part 30 are printed in chamber
12 (or at least in a locally-heated deposition region) that is
maintained at a temperature between a solidification temperature
and the cold crystallization temperature T.sub.c,cold of the part
material. This can anneal the successively-printed printed layers,
allowing them to cool down and solidify slowly, which can partially
relieve the residual stresses.
[0066] In some embodiments, chamber 12 or the locally-heated
deposition region is maintained at a temperature between a
solidification temperature and the glass transition temperature
T.sub.g of the part material. These embodiments are suitable for
part materials having low levels of crystalline regions, where the
crystalline regions are not capable of supporting the printed
layers at higher temperatures without slumping.
[0067] Alternatively, in other embodiments, chamber 12 or the
locally-heated deposition region is maintained at a temperature
within an annealing window 84 having a lower limit at about the
glass transition temperature T.sub.g of the part material and an
upper limit that is less than the cold crystallization temperature
T.sub.c,cold of the part material. In particular, annealing window
84 preferably encompasses the plateau region 86 of DSC heating
curve 80, which is above the increased slope for the glass
transition temperature T.sub.g and below the decreased slope for
the cold crystallization temperature T.sub.c,cold. These
embodiments are suitable for part materials having enough
crystalline regions to support the printed layers without slumping,
despite being held above the glass transition temperature T.sub.g
of the part material.
[0068] In further embodiments, such as for use with low-temperature
materials (e.g., those with glass transition temperatures near
ambient temperatures), chamber 12 may be omitted, and the part
material may be printed at room temperature (e.g., 25.degree. C.).
Regardless of the annealing temperature, it has been found that the
substantially-miscible blends for the part material modify the
glass transition temperature T.sub.g of the part material from that
of the amorphous polymer(s), typically flowing the Flory-Fox
Equation. The substantially-miscible blends may also decrease the
hot crystallization temperature T.sub.c,hot of the part material
from that of the pure semi-crystalline polymer(s). This provides a
unique advantage in that the cumulative amount of crystallization
for the part material upon cooling can be reduced, which
accordingly allows the printed layers of the part material to have
low levels of crystallinity.
[0069] In particular, upon being extruded and deposited from nozzle
48, the part material preferably is quickly cooled down past its
hot crystallization temperature T.sub.c,hot to its annealing
temperature below the cold crystallization temperature T.sub.c,cold
of the part material (e.g., within annealing window 84). This
effectively supercools the part material down below its cold
crystallization temperature T.sub.c,cold.
[0070] It has been found that the level of crystallinity can be
controlled based on the particular annealing temperature used. For
instance, if more amorphous properties are desired, the annealing
temperature may be set to be set within about 5.degree. C. of the
glass transition temperature T.sub.g of the part material.
Alternatively, if more crystalline properties are desired, the
annealing temperature may be set to be set within 5.degree. C. of
the cold crystallization temperature T.sub.c,cold of the part
material. Furthermore, any intermediate amorphous-crystalline
variation may be achieved by maintaining the annealing temperature
at a selected temperature within annealing window 84.
[0071] The incorporation of the amorphous polymer(s) also assists
in physically impeding the semi-crystalline polymer(s) from
grouping together in ordered arrangements to form crystalline
regions. As such, as the part material quickly cools down from its
melting temperature T.sub.m, the short residence time in the region
between its hot crystallization temperature T.sub.c,hot and its
cold crystallization temperature T.sub.c,cold, combined with the
crystallization impedance, preferably minimizes or otherwise
reduces the formation of crystalline regions in the part
material.
[0072] For instance, if a given pure semi-crystalline polymer
(i.e., non-blend) is capable of crystallizing to its fullest extent
in about 3 seconds in the region between its hot crystallization
temperature T.sub.c,hot and its cold crystallization temperature
T.sub.c,cold, and if it quickly cools down such that it resides in
this region for about one second, it may form about one-third of is
achievable of crystalline regions. In comparison, the
crystallization impedance of the part material blend may require
more than a 10 to 20-fold increase in the time required to fully
crystallize. As such, when the part material resides in this region
between its hot crystallization temperature T.sub.c,hot and its
cold crystallization temperature T.sub.c,cold for about one second,
it may only form about 1-3% of its fully-achievable crystallinity,
for example. In fact, it has been observed that the supercooled
part material exhibits a translucent, substantially non-opaque
appearance. This is an indication that crystallinity has been
significantly retarded since crystalline regions typically modify
the indices of refraction of the extruded layers to render them
opaque.
[0073] The minimized or reduced crystallization correspondingly
reduces the discontinuous changes in volume of the semi-crystalline
polymer(s), thereby reducing the residual stresses on the printed
layers. Furthermore, holding the printed layers at the annealing
temperature (e.g., within annealing window 84) also anneals the
successively-printed printed layers, allowing them to cool down and
solidify slowly, which can relieve the residual stresses typically
associated with amorphous materials.
[0074] In other words, the part material is preferably supercooled
quickly from its extrusion temperatures down to an annealing
temperature in annealing window 84, and then held within annealing
window 84 for a suitable duration to relieve the residual stresses.
After that, the printed layers of the part material may be cooled
down further (e.g., below its glass transition temperature T.sub.g
and/or its solidification temperature).
[0075] Another interesting property of the part materials of the
present disclosure is that, despite the minimized or reduced
crystallinity, the crystallization that does occur during the
supercooling generates a sufficient amount of heat to induce extra
or increased molecular reptation at the extrudate-part interface.
In other words, the heat produced during the limited
crystallization-exothermic reaction allows the polymer molecules at
the extrudate-part interface to move and become highly entangled.
It has been observed that, due to the heat of fusion of the
extruded roads, the rate of temperature decay of the extruded part
material can change, and cool down at a slower rate. For example,
in an interior raster pattern, this can result in an interfacial
temperature boost, causing better reptation in the X-Y build plane,
as long as the rastered roads contact each other before the
extruded part material cools down to the annealing temperature in
chamber 12. This accordingly increases the strength of the printed
3D part 30 in both the intra-layer x-y directions, and also in the
interlayer z-direction. As a result, 3D part 30 may have mechanical
properties (e.g., strengths and ductilities) similar to those of
semi-crystalline polymer(s).
[0076] Once the printing operation is completed, 3D part 30 may
then be cooled down to room temperature and optionally undergo one
or more post-printing processes. Alternatively, 3D part 30 may be
reheated in a post-printing crystallization step. In this step, 3D
part 30 may be heated up to about its cold crystallization
temperature T.sub.c,cold for a sufficient duration to induce
further crystallization of the semi-crystalline polymer(s).
Examples of suitable annealing durations in the post-printing
crystallization step range from about 30 minutes to 3 hours, and
may vary depending on the dimensions of each 3D part 30 and the
part material compositions. Correspondingly, examples of suitable
annealing temperatures in the post-printing crystallization step
range from about the cold crystallization temperature T.sub.c,cold
of the part material to within about 10.degree. C. above its cold
crystallization temperature T.sub.c,cold, and more preferably to
within about 5.degree. C. above its cold crystallization
temperature T.sub.c,cold.
[0077] The post-printing crystallization step can further increase
the mechanical, thermal, and chemical resistance properties of 3D
part 30 due to the increased formation of the crystalline regions.
Additionally, this post-printing crystallization step is performed
on 3D part 30 as a whole (i.e., congruent crystallization), rather
than as the layers are individually printed. As such, any potential
shrinkage on 3D part 30 from the formation of the crystalline
regions occurs in a uniform manner similar to the effects in an
injection molding process, rather than in a layer-by-layer manner
that can otherwise result in curling effects. Another important
feature with the post-printing crystallization step is that 3D part
30 is preferably de-coupled from platen 14 (e.g., from a build
sheet of platen 14), allowing 3D part 30 to be further crystallized
without being restricted by any non-shrinkable build sheet.
[0078] As mentioned above, a 3D part 30 having a translucent,
substantially non-opaque appearance is an indication that
crystallinity has been retarded during the printing operation.
Similarly, the transformation from the translucent, substantially
non-opaque appearance to an opaque appearance is an indication that
the part material of 3D part 30 has undergone significant
crystallization in the post-printing crystallization step. After
the post-printing crystallization step is completed, the resulting
3D part 30 may then be cooled down to room temperature and
optionally undergo one or more post-printing processes.
[0079] The post-printing crystallization step may be performed in
chamber 12 of system 10, or alternatively in a separate annealing
oven. A separate annealing oven may be preferred in many
situations, such as when support structure 32 needs to be removed
prior to the post-printing annealing step and/or when system 10
needs to be used for subsequent printing operations. For example, a
printing farm of multiple systems 10 may operate in coordination
with one or more separate annealing ovens to maximize the duty
cycles of the systems 10.
[0080] The above-discussed control of the crystallization kinetics
of the part material requires the part material to have a blend of
one or more semi-crystalline polymers and one or more secondary
materials, preferably amorphous polymer(s), that retard
crystallization of the semi-crystalline polymer(s) and that are at
least partially miscible (or more preferably, substantially
miscible) with the semi-crystalline polymer(s).
[0081] Preferably the semi-crystalline polymer(s) and the secondary
material(s) in the blend are separate compounds (e.g., separate
polymers) that are homogenously blended. However, in alternative
(or additional) embodiments, part material may include one or more
copolymers having chain segments corresponding to the
semi-crystalline polymer(s) and the secondary material(s), where
the chain segments of the secondary material(s) retard the
crystallization of the chain segments of the semi-crystalline
polymeric material(s).
[0082] In a first embodiment, the part material is a polyamide part
material that compositionally includes a polyamide blend of one or
more semi-crystalline polyamides, one or more amorphous polyamides,
and optionally, one or more additives dispersed in the polyamide
blend. The semi-crystalline polyamide(s) may include polyamide
homopolymers and copolymers derived from monomers that include
caprolactam, diamines in combination with monomers that include
dicarboxylic acids, and mixtures thereof. The diamine monomers and
the dicarboxylic acid monomers are each preferably aliphatic
monomers, and more preferably are each acyclic aliphatic
monomers.
[0083] However, in other embodiments, the diamine monomers and/or
the dicarboxylic acid monomers may include aromatic or
cycloaliphatic groups while maintaining crystalline domains.
Furthermore, in some embodiments, the semi-crystalline polyamide(s)
may include cyclic groups in grafted pendant chains (e.g., maleated
groups), as discussed below. Preferred polyamide homopolymers and
copolymers for the semi-crystalline polyamide(s) may be represented
by the following structural formulas:
##STR00001##
where R.sub.1, R.sub.2, and R.sub.3 may each be a hydrocarbon chain
having 3-12 carbon atoms. The hydrocarbon chains for R.sub.1,
R.sub.2, and R.sub.3 may be branched (e.g., having small alkyl
groups, such as methyl groups) or unbranched, and which are
preferably aliphatic, acyclic, saturated hydrocarbon chains.
[0084] As used herein, reference to a repeating unit identifier "n"
in a polymer structural formula means that the bracketed formula
repeats for n units, where n is a whole number that may vary
depending on the molecular weight of the given polymer.
Furthermore, the particular structures of the bracketed formulas
may be the same between the repeating units (i.e., a homopolymer)
or may be vary between the repeating units (i.e., copolymer). For
example, in the above-shown Formula 1, R.sub.1 may be the same
structure for each repeating unit to provide a homopolymer, or may
be two or more different structures that repeat in an alternating
copolymer manner, a random copolymer manner, a block copolymer
manner, a graft copolymer manner (as discussed below), or
combinations thereof.
[0085] Preferred polyamides for the semi-crystalline polyamide(s)
include nylon-type materials such as polycarpolactum (PA6),
polyhexamethyleneaidpamide (PA6,6), polyhexamethylenenonamide
(PA6,9), polyhexamethylenesebacamide (PA6,10), polyenantholactum
(PA7), polyundecanolactum (PA11), polylaurolactam (PAl2), and
mixtures thereof. More preferably, the polyamides for the
semi-crystalline polyamide(s) include PA6; PA6,6; and mixtures
thereof. Examples of suitable semi-crystalline polyamide(s) having
aromatic groups include semi-crystalline polyamides of aliphatic
diamines and isophthalic acid and/or terephthalic acid (e.g.,
semi-crystalline polyphthalamides).
[0086] Furthermore, in some embodiments, at least a portion of the
semi-crystalline polyamide(s) are graft semi-crystalline
polyamide(s), each having a polyamide backbone and one or more
impact modifiers grafted to the backbone. The impact modifiers may
include polyolefin-chain monomers and/or elastomers having coupling
groups configured to graft the monomers to the polyamide backbone.
Suitable coupling groups for the impact modifiers include
piperidine groups, acrylic/methacrylic acid groups, maleic
anhydride groups, epoxy groups.
[0087] Preferred coupling groups include maleic anhydride groups
and epoxy groups, such as those respectively represented by the
following structural formulas:
##STR00002##
where R.sub.4 and R.sub.5 may each be a hydrocarbon chain having
2-20 carbon atoms, and more preferably 2-10 carbon atoms; and where
R.sub.6 may be a hydrocarbon chain having 1-4 carbon atoms. The
hydrocarbon chains of R.sub.4, R.sub.5, and R6 may each be branched
or unbranched. For example, preferred impact modifiers include
maleated polyethylenes, maleated polypropylenes, and mixtures
thereof. In embodiments in which the impact modifier includes an
elastomer, preferred impact modifiers include maleated ethylene
propylene diene monomers (EPDM).
[0088] Examples of suitable commercial impact modifiers include
those available under the tradenames LOTADER from Arkema Inc.,
Philadelphia, Pa.; those under the tradename ELVALOY PTW, FUSABOND
N Series, and NUCREL from E. I. du Pont de Nemours and Company,
Wilmington, Del.; and those under the tradename ROYALTURF from
Chemtura Corporation, Philadelphia, Pa. Examples of preferred graft
semi-crystalline polyamides include those commercially available
under the tradename ULTRAMID from BASF Corporation, Florham Park,
N.J.; and those under the tradename GRILAMID from EMS-Chemie, Inc.,
Sumter, S.C. (business unit of EMS-Grivory).
[0089] The grafted impact modifiers may constitute from about 1% to
about 20% by weight of the graft semi-crystalline polyamide(s). In
some embodiments, the grafted impact modifiers constitute from
about 5% to about 15% by weight of the graft semi-crystalline
polyamide(s). In embodiments that incorporate the graft
semi-crystalline polyamide(s), the graft semi-crystalline
polyamide(s) may constitute from about 50% to 100% by weight of the
semi-crystalline polyamide(s) in the part material, more preferably
from about 80% to 100% by weight, and even more preferably from
about 95% to 100% by weight. In some preferred embodiments, the
semi-crystalline polyamide(s) of the PA material consist
essentially of the graft semi-crystalline polyamide(s).
[0090] The semi-crystalline polyamide(s) preferably have a
molecular weight range that renders them suitable for extrusion
from print head 18, which may be characterized by their melt flow
indices. Preferred melt flow indices for the semi-crystalline
polyamide(s) range from about 1 gram/10 minutes to about 40
grams/10 minutes, more preferably from about 3 grams/10 minutes to
about 20 grams/10 minutes, and even more preferably from about 5
grams/10 minutes to about 10 grams/10 minutes where the melt flow
index, as used herein, is measured pursuant to ASTM D1238-10 with a
2.16 kilogram weight at a temperature of 260.degree. C.
[0091] The PA material also compositionally includes one or more
amorphous polyamides that are preferably miscible with the
semi-crystalline polyamide(s). The amorphous polyamide(s) may
include polyamide homopolymers and copolymers derived from monomers
that include diamines in combination with monomers that include
dicarboxylic acids, which are preferably cycloaliphatic and/or
aromatic monomers. However, in other embodiments, the diamine
monomers and/or the dicarboxylic acid monomers may include
aliphatic groups (e.g., acyclic aliphatic groups) while maintaining
amorphous properties.
[0092] Preferred polyamide homopolymers and copolymers for the
amorphous polyamide(s) may be represented by the following
structural formulas:
##STR00003##
where R.sub.7 and R.sub.10 may each be a hydrocarbon chain having
3-12 carbon atoms. The hydrocarbon chains for R.sub.7 and R.sub.10
may be branched (e.g., having small alkyl groups, such as methyl
groups) or unbranched, and which are preferably aliphatic, acyclic,
saturated hydrocarbon chains. In comparison, R.sub.8, R.sub.9,
R.sub.11, and R.sub.12 may each be a hydrocarbon chain having 5-20
carbon atoms, which may be branched (e.g., having alkyl groups,
such as methyl groups) or unbranched, and each of which includes
one or more aromatic groups (e.g., benzene groups), one or more
cycloaliphatic groups (e.g., cyclohexane groups), or combinations
thereof.
[0093] Preferred polyamides for the amorphous polyamide(s) include
nylon-type materials such as polyamides of hexamethylenediamine,
isophthalic acid, terephthalic acid, and adipic acid (PA6i/6T);
polyamides of PA2; 3,3-dimethyl-4,4-diaminodicyclohexylmethane, and
isophthalic acid (PA12/MACMI); polyamides of PA12;
3,3-dimethyl-4,4-diaminodicyclohexylmethane, and terephthalic acid
(PA12/MACMT); (PA12/MACMI/MACMT); PA6i; PA12/MACM36; PANDT/INDT;
polyamides of trimethylhexamethylenediamine and terephthalic acid
(PA6/3T); polyamides of cycloaliphaticdiamine and dodecanedioic
acid; amorphous polyamides of aliphatic diamines and isophthalic
acid and/or terephthalic acid (e.g., amorphous polyphthalamides);
and mixtures thereof. More preferably, the polyamides for the
amorphous polyamide(s) include PA6/3T, polyamides of
cycloaliphaticdiamine and dodecanedioic acid, and mixtures
thereof.
[0094] In some embodiments, at least a portion of the amorphous
polyamide(s) may be graft amorphous polyamide(s), each having a
polyamide backbone and one or more impact modifiers grafted to the
backbone. Preferred impact modifiers for grafting to the amorphous
polyamide(s) include those discussed above for the graft
semi-crystalline polyamide(s), such as polyolefin-chain monomers
and/or elastomers having coupling groups configured to graft the
monomers to the polyamide backbone (e.g., piperidine groups,
acrylic/methacrylic acid groups, maleic anhydride groups, and epoxy
groups). Suitable concentrations of the grafted impact modifiers in
the graft amorphous polyamide(s), and suitable concentrations of
the graft amorphous polyamides relative to the entirety of
amorphous polyamide(s) in the part material include those discussed
above for the graft semi-crystalline polyamide(s).
[0095] Preferred concentrations of the amorphous polyamide(s) in
the polyamide blend range from about 30% to about 70% by weight,
more preferably from about 40% to about 60% by weight, and even
more preferably from about 45% to about 55% by weight, where the
semi-crystalline polyamide(s) constitute the remainder of the
polyamide blend. Accordingly, preferred ratios of the amorphous
polyamide(s) to the semi-crystalline polyamide(s) range from about
3:7 to about 7:3, more preferably from about 4:6 to about 6:4, and
even more preferably from about 4.5:5.5: to about 5.5:4.5.
[0096] In a second embodiment, the part material includes a
substantially miscible blend of one or more polyetherimides (PEI)
and one or more semi-crystalline polyaryletherketones (PAEK), such
as one or more polyetherketones (PEK), polyetheretherketones
(PEEK), polyetherketoneketones (PEKK), polyetheretherketoneketones
(PEEKK), polyetherketoneether-ketoneketones (PEKEKK), mixtures
thereof, and the like, and more preferably one or more
polyetheretherketones (PEEK). Preferred concentrations of the
polyaryletherketone(s) in this blend range from about 35% by weight
to about 99% by weight, and more preferably from about 50% by
weight to about 90% by weight, and even more preferably form about
60% by weight to about 80% by weight, where the polyetherimide(s)
constitute the remainder of the blend.
[0097] In a third embodiment, the part material includes a
substantially miscible blend of one or more polyphenylsulfones
(PPSU), polysulfones (PSU), and/or polyethersulfones (PES), with
one or more semi-crystalline polyaryletherketones. Preferred
concentrations of the
polyphenylsulfone(s)/polysulfone(s)/polyethersulfone(s) in this
blend range from about 1% by weight to about 65% by weight, and
more preferably from about 20% by weight to about 50% by weight,
where the polyaryletherketone(s) constitute the remainder of the
blend.
[0098] In a fourth embodiment, the part material includes a
substantially miscible blend of one or more polycarbonates and one
or more semi-crystalline polybutylene terephthalates (PBT) and/or
one or more semi-crystalline polyethylene terephthalates (PET).
Preferred concentrations of the polycarbonate(s) in this blend
range from about 30% by weight to about 90% by weight, and more
preferably from about 50% by weight to about 70% by weight, where
the polybutylene terephthalate(s)/polyethylene terephthalate(s)
constitute the remainder of the blend.
[0099] In a fifth embodiment, the part material includes a
substantially miscible blend of one or more amorphous polyethylene
terephthalates (e.g., glycol-modified polyethylene terephthalates)
and one or more semi-crystalline polyethylene terephthalates.
Preferred concentrations of the amorphous polyethylene
terephthalate(s) in this blend range from about 10% by weight to
about 40% by weight, and more preferably from about 15% by weight
to about 25% by weight, where the semi-crystalline polyethylene
terephthalate(s) constitute the remainder of the blend.
[0100] In a sixth embodiment, the part material includes a
substantially miscible blend of one or more amorphous
polyaryletherketones and one or more semi-crystalline
polyaryletherketones, such as one or more amorphous
polyetherketoneketones (PEKK) and one or more semi-crystalline
polyetherketoneketones (PEKK). Preferred concentrations of the
amorphous polyaryletherketones(s) in this blend range from about
30% by weight to about 90% by weight, and more preferably from
about 50% by weight to about 70% by weight, where the
semi-crystalline polyaryletherketones(s) constitute the remainder
of the blend.
[0101] In some embodiments, the part material may also include
additional additives, such as colorants, fillers, plasticizers,
impact modifiers, and combinations thereof. In embodiments that
include colorants, preferred concentrations of the colorants in the
part material range from about 0.1% to about 5% by weight. Suitable
colorants include titanium dioxide, barium sulfate, carbon black,
and iron oxide, and may also include organic dyes and pigments.
[0102] In embodiments that include fillers, preferred
concentrations of the fillers in the part material range from about
1% to about 45% by weight for some fillers (e.g., glass and carbon
fillers), and up to about 80% by weight for other fillers, such as
metallic and ceramic fillers. Suitable fillers include calcium
carbonate, magnesium carbonate, glass spheres, graphite, carbon
black, carbon fiber, glass fiber, talc, wollastonite, mica,
alumina, silica, kaolin, silicon carbide, zirconium tungstate,
soluble salts, metals, ceramics, and combinations thereof.
[0103] In the embodiments including the above-discussed additional
additives, the polymer blend preferably constitutes the remainder
of the part material. As such, the polymer blend may constitute
from about 55% to 100% by weight of the part material, and more
preferably from about 75% to 100% by weight. In some embodiments,
the polymer blend constitutes from about 90% to 100% by weight of
the part material, more preferably from about 95% to 100% by
weight. In further embodiments, the part material consists
essentially of the polymer blend, and optionally, one or more
colorants and/or anti-oxidants.
[0104] Preferably, the polymer blend is also substantially
homogenous, allowing each portion of the part material used in an
additive manufacturing system to consistently exhibit the same
thermal and physical properties. For example, with system 10 having
print head 18, the flow rate of the molten part material (i.e.,
melt 70) from nozzle 48 is controlled by the rate at which filament
52 enters liquefier tube 56, and the melting rate of filament 52
within heating zone 68. System 10 may operate with preset
instructions for extruding melt 70 at desired flow rates based on
tool path geometries. These preset instructions are preferably
based on the thermal properties of the part material, namely the
melting rate and viscosity of the part material, as well as the
crystallization kinetics of the part material.
[0105] As such, if the polymer blend were otherwise non-homogenous,
the part material would not be uniform. This could cause successive
segments of filament 52 to melt at different rates, affecting the
height of meniscus 74. This accordingly can change the extrusion
rate of melt 70 from the preset instructions, which can impair part
quality in 3D part 30. Additionally, a non-homogenous blend may
result in imbalances in the crystallization kinetics of the part
material, which could reduce the above-discussed benefits of
controlling the crystallization kinetics. Accordingly, filament 52
is preferably manufactured from a part material having a
substantially homogenous polymer blend of the semi-crystalline
polymer(s) and the secondary material(s) (e.g., amorphous
polymer(s)). In embodiments that include one or more additives, the
additive(s) are preferably dispersed in the polymer blend in a
substantially uniform manner.
[0106] As mentioned above, the above-discussed method may also be
utilized with electrophotography-based additive manufacturing
systems and selective laser sintering systems. With respect to
electrophotography-based additive manufacturing systems, the part
material may be provided in powder form for use in an
electrophotography-based additive manufacturing system, such as
those disclosed in Hanson et al., U.S. Publication Nos.
2013/0077996 and 2013/0077997, and Comb et al., U.S. Publication
Nos. 2013/0186549 and 2013/0186558, the disclosures of which are
incorporated by reference to the extent that they do not conflict
with the present disclosure.
[0107] As discussed in these references, the
electrophotography-based additive manufacturing systems preferably
operate with layer transfusion assemblies that transfuse each
successively-developed layer based on interlayer polymer
entanglement (i.e., reptation). As such, the above-discussed method
for controlling the crystallization kinetics of the part material
for the extrusion-based additive manufacturing systems may also be
used in the same manner with the electrophotography-based additive
manufacturing systems.
[0108] In comparison, however, selective laser sintering systems
may print 3D parts from nylon materials in a manner in which a
nylon material is held in a gelatinous, undercooled amorphous state
between the melting temperature and the hot crystallization
temperature of the nylon material. However, nylon materials
typically have small temperature windows between their melting
temperatures and the hot crystallization temperatures, rendering it
difficult to hold the printed layers in this amorphous state after
being melted with a laser beam.
[0109] However, as discussed above, it has been found that the
substantially miscible blends for the part material of the present
disclosure decrease the hot crystallization temperature T.sub.c,hot
of the part material from that of the semi-crystalline polymer(s).
Conversely, the melting temperature T.sub.m of the part material
remains substantially unchanged. As such, the substantially
miscible blend for the part material widens the operating window,
referred to as operating window 88 in FIG. 4, in which the printed
layers may be held in the gelatinous, undercooled amorphous state
to prevent warping and distortions. In this case, the powder
materials may be selectively melted with the laser beam and held
within this operating window 88 until the printing operation is
completed. The whole 3D part 30 may then be cooled down in a
conventional manner.
[0110] In embodiments involving the above-discussed technique used
in a selective laser sintering system (e.g., systems disclosed in
Deckard, U.S. Pat. Nos. 4,863,538 and 5,132,143), the part material
may be provided in powder form for use in other powder-based
additive manufacturing systems. In some alternative embodiments,
such as with some polyamide materials (e.g., glass-filled PA6/10
materials), this technique may also be utilized in extrusion-based
and/or electrophotography-based additive manufacturing systems.
This can accordingly produce 3D parts having high heat deflection
temperatures, which can be beneficial for use with soluble support
materials.
EXAMPLES
[0111] The present disclosure is more particularly described in the
following examples that are intended as illustrations only, since
numerous modifications and variations within the scope of the
present disclosure will be apparent to those skilled in the art.
Unless otherwise noted, all parts, percentages, and ratios reported
in the following examples are on a weight basis, and all reagents
used in the examples were obtained, or are available, from the
chemical suppliers described below, or may be synthesized by
conventional techniques.
I. Examples 1-4
[0112] Part materials of Examples 1-4 and Comparative Examples A
and B were prepared as PEEK/PEI blends with varying weight ratios.
Each part material was then analyzed using DSC to determine the
glass transition temperature T.sub.g, cold crystallization
temperature T.sub.c,cold, melting temperature T.sub.m, and hot
crystallization temperature T.sub.c,hot. Table 1 lists the DSC
results for the tested part materials with the PEEK/PEI ratios,
where the temperatures were reported in degrees Celsius.
TABLE-US-00001 TABLE 1 PEEK/PEI Weight T.sub.c, cold T.sub.m
T.sub.c, hot Example Ratio T.sub.g (peak) (peak) (peak) Comparative
Example A 100/0 146 -- 346 303 Example 1 85/15 160 207 341 288
Example 2 70/30 179 249 338 265 Example 3 55/44 181 265 337 266
Example 4 35/65 191 -- 338 -- Comparative Example B 0/100 214 -- --
--
[0113] The results in Table 1 show the relative changes in the
glass transition temperature T.sub.g, cold crystallization
temperature T.sub.c,cold, melting temperature T.sub.m, and hot
crystallization temperature T.sub.c,hot for the different PEEK/PEI
ratios. For example, the glass transition temperature T.sub.g
increases substantially with the increased concentration of PEI.
Furthermore, the cold crystallization temperature T.sub.c,cold and
the hot crystallization temperature T.sub.c,hot converged closer
together with the increased concentration of PEI, but the melting
temperature T.sub.m remained relatively the same (e.g., 4 degree
drop between Examples 1 and 3, versus a 22 degree drop for the hot
crystallization temperature T.sub.c,hot).
[0114] Accordingly, the differences between the glass transition
temperatures T.sub.g and the cold crystallization temperatures
T.sub.c,cold for Examples 1-3 provide suitable annealing windows
(e.g., annealing window 84) for printing 3D parts with
extrusion-based and/or electrophotography-based additive
manufacturing systems. Similarly, the differences between the
melting temperatures T.sub.m and the hot crystallization
temperature T.sub.c,hot for Examples 1-3 provide suitable operating
windows (e.g., operating window 88) for printing 3D parts with
selective laser sintering systems.
[0115] The DSC testing also involved reheating the part materials
after the cooling step to simulate a post-printing crystallization
step. During this reheating step, the part materials of Examples 2
and 3 each exhibited two different glass transition temperatures
T.sub.g. The part material of Example 2 had a first glass
transition temperature of 164.degree. C. and a second glass
transition temperature of 209.degree. C. The part material of
Example 2 had a first glass transition temperature of 167.degree.
C. and a second glass transition temperature of 210.degree. C. This
phenomenon is believed to be caused by the PEEK and PEI polymers
separating upon crystallization, such that the PEI was not
incorporated in the PEEK crystalline regions.
[0116] The enthalpy of fusions at the hot crystallization
temperature T.sub.c,hot for the part materials were also
determined, as listed below in Table 2.
TABLE-US-00002 TABLE 2 PEEK/PEI Enthalpy of Weight Fusion Example
Ratio (Joules/gram) Comparative Example A 100/0 56 Example 1 85/15
43 Example 2 70/30 37 Example 3 55/44 37 Example 4 35/65 3
Comparative Example B 0/100 --
[0117] The results in Table 2 show that the part materials of
Examples 1-3 exhibit high levels of exothermic energy upon
crystallization. The part material of Example 4 appeared to
generate very little crystallization. However, this is believed to
be due to a kinetic phenomenon that would disappear with slower
cooling. The part material of Example 4 exhibited a melting point
(as shown above in Table 1) and turned opaque upon reheating (i.e.,
re-crystallization).
II. Example 5
[0118] A part material of Example 5 having a PEEK/PEI weight ratio
of 60/40 was compounded into cylindrical filaments having an
average diameter of about 0.07 inches and wound onto spools of
consumable assemblies. For each run, the consumable assembly was
loaded to an extrusion-based additive manufacturing system
commercially available from Stratasys, Inc., Eden Prairie, Minn.
under the trademarks "FDM" and "FORTUS 400mc". The filament was
then fed from the consumable assembly to print head liquefier
assembly of the system, melted, and extruded from print head nozzle
to print 3D parts in a heated chamber maintained at 160.degree. C.
(i.e., below its glass transition temperatures T.sub.g).
[0119] FIG. 5 illustrates pellets and the printed 3D parts from the
part material of Example 5. The printed 3D part and associated
pellets exhibited a golden, translucent appearance due to the low
levels of crystallinity. A corresponding 3D part and portions of
the pellets were also reheated to about 200.degree. C. (i.e., a
post-printing crystallization process) for a sufficient duration to
re-crystallize the PEEK in the part material. As shown, the
annealed 3D part and pellets each exhibited an opaque appearance,
which was more tan/whitish in color than the golden color of the
non-re-crystallized part/pellets.
III. Example 6
[0120] Part materials of Example 6 were prepared as polyamide
blends, where the semi-crystalline polyamide was a graft PA12
polyamide commercially available under the tradename GRILAMID L16
from EMS-Chemie, Inc., Sumter, S.C. (business unit of EMS-Grivory),
and the amorphous polyamide was a PA12 polyamide commercially
available under the tradename GRILAMID TR90 from EMS-Chemie, Inc.,
Sumter, S.C. (business unit of EMS-Grivory).
[0121] For each part material of Example 6, the semi-crystalline
polyamide concentration in the part material ranged from
27.2%-28.2% by weight, and the amorphous polyamide concentration in
the part material ranged from 65.2%-66.2% by weight, for a blend
ratio of about 70:30 of the amorphous polyamide to semi-crystalline
polyamide. The part material also included an impact modifier
having a concentration in the part material ranging from 4.5%-5.5%
by weight, and an anti-oxidant having a concentration in the part
material ranging from 0.03%-0.13% by weight.
[0122] Each part material of Example 6 was analyzed using DSC to
provide an average glass transition temperature T.sub.g of
55.degree. C., an average cold crystallization temperature
T.sub.c,cold of 130.degree. C., an average melting temperature
T.sub.m of 178.degree. C., and an average hot crystallization
temperature T.sub.c,hot of 148.degree. C. Each part material was
also compounded into cylindrical filaments having an average
diameter of about 0.07 inches and wound onto spools of consumable
assemblies.
[0123] For each run, the consumable assembly was loaded to an
extrusion-based additive manufacturing system commercially
available from Stratasys, Inc., Eden Prairie, Minn. under the
trademarks "FDM" and "FORTUS 400mc". The liquefier temperature was
set to 355.degree. C. and the heated chamber temperature was set to
80.degree. C., 100.degree. C., or 120.degree. C., depending on the
3D part geometry being printed. Each 3D part exhibited good
dimensional stability and low levels of crystallinity.
IV. Examples 7 and 8
[0124] A part materials of Example 7 was prepared as an
impact-modified PET blend, where the semi-crystalline PET was a
polyethylene terephthalate copolymer commercially available under
the tradename "SKYPET BR" from SK Chemicals, South Korea, and the
amorphous PET was a glycol-modified polyethylene terephthalate
commercially available under the tradename "SKYGREEN S2008" from SK
Chemicals, South Korea. The part material included 76% by weight of
the semi-crystalline PET, 19% by weight of the amorphous PET, and
5% by weight of an impact modifier commercially available under the
tradename "ELVALOY PTW" from E.I. du Pont de Nemours and Company,
Wilmington, Del.
[0125] The part material of Example 7 was compounded into
cylindrical filaments having an average diameter of about 0.07
inches and wound onto spools of consumable assemblies. For each
run, the consumable assembly was loaded to an extrusion-based
additive manufacturing system commercially available from
Stratasys, Inc., Eden Prairie, Minn. under the trademarks "FDM" and
"FORTUS 400mc".
[0126] During the printing operations, the filament was melted and
extruded from a print head at a temperature of 320.degree. C. into
a heated build chamber, where the temperature of the build chamber
was held at 90.degree. C., 100.degree. C., 110.degree. C., and
120.degree. C. for four different runs. The part material had a
glass transition temperature of about 78.degree. C. As such, these
different temperatures tested how the different annealing windows
affected the level of crystallinity in the resulting 3D part.
[0127] After being printed, each of the four 3D parts was slowly
heated and the resulting modulus was measured, as illustrated in
FIG. 6. As shown in FIG. 6, the part material annealed at
90.degree. C. maintained a mostly-amorphous mechanical behavior,
while the part material annealed at 120.degree. C. maintained a
mostly-semi-crystalline mechanical behavior. The part materials
annealed at 100.degree. C. and 110.degree. C. fell between these
two end points.
[0128] As can be seen, over a heated chamber temperature range of
about 30 degrees Celsius, the dynamic mechanical behavior of the
tested part materials changed significantly from almost mostly
amorphous to almost mostly crystalline. This is further illustrated
by the tan-delta peak onset in FIG. 7, where the peak onset
occurred later as the temperature in the heated chamber increased,
which corresponded to a more crystalline 3D part. Accordingly,
these results confirm that the extent of crystallization in the
resulting 3D part for the part materials can be controlled by a
properly-selected annealing window.
[0129] The part material of Example 8 included 70% by weight of the
PET blend of Example 7 and 30% by weight of a glass-based filler.
The part material of Example 8 was also printed as discussed above
for the part materials of Example 6, where the heated chamber was
held at only 80.degree. C. to maintain a mostly-amorphous
mechanical behavior. A portion of the 3D part samples were then
reheated to about 135.degree. C. (i.e., a post-printing
crystallization process) for a sufficient duration to
re-crystallize the semi-crystalline PET in the part material.
[0130] After being printed, each 3D part sample was then slowly
heated and the resulting modulus was measured, as illustrated in
FIG. 8, which also compares the results of the part material for
Example 7 printed in the 120.degree. C. heated chamber. As shown in
FIG. 8, the post-printing crystallization process significantly
increased the crystallinity of the part material compared to the
initial samples.
[0131] Although the present disclosure has been described with
reference to preferred embodiments, workers skilled in the art will
recognize that changes may be made in form and detail without
departing from the spirit and scope of the disclosure.
* * * * *